CN103350545B - A kind of biaxial tension nylon composite membrane and preparation method thereof - Google Patents
A kind of biaxial tension nylon composite membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of biaxial tension composite membrane, have following structure: the first nylon layer, the second nylon layer, evoh layer, the 3rd nylon layer and the 4th nylon layer, described each layer is all through biaxial tension; Wherein, described first nylon layer and the 4th nylon layer are made up of nylon 95 ~ 100% and additive 0 ~ 5%, and described additive is a kind of in opening agent, slipping agent, antistatic additive or their combination; Described second nylon layer and the 3rd nylon layer are the nylon of 100%; Described evoh layer is the EVOH of 100%.Meanwhile, the invention still further relates to a kind of preparation method of biaxial tension EVOH/ coextrusion nylon film.
Description
technical field:
The present invention relates to a kind of biaxial tension composite membrane and preparation method thereof, particularly relate to a kind of biaxial tension EVOH/ nylon high-barrier composite membrane and preparation method thereof.
background technology:
The features such as it is large that BON biaxially oriented nylon film has mechanical strength, and the transparency is excellent, have higher barrier property, have a wide range of applications in fields such as packagings for foodstuff.But the barrier property of nylon belongs to medium level in all barrier materials, actual needs still cannot be met at the special dimension that ask for something is higher.
EVOH(ethylene-vinyl alcohol copolymer) be a kind of high barrier material, there is the chain structure of highly crystalline, integrate the barrier property of the good processability of ethene polymers and vinyl alcohol polymer excellence, the different manifestations along with ethylene contents goes out different processing characteristicies and barrier property.Its barrier property is only second to aluminium foil, and its gas barrier property is tens times of PVDC, more than 100 times of nylon especially.But EVOH also has some shortcomings, as its gas barrier property at high humidity declines serious, process more difficult, under the effect of heat and stress, EVOH is very easy to crystallization, makes stretching become abnormal difficult simultaneously.
summary of the invention:
Scope of the present invention, only by claims defined, any degree is not subject to the restriction of this joint institute those set forth.
The object of the present invention is to provide and a kind ofly there is excellent mechanical performance and barrier property and be easy to coextrusion nylon film processed and preparation method thereof.
The present invention proposes a kind of biaxial tension EVOH/ coextrusion nylon film, has following structure: the first nylon layer, the second nylon layer, evoh layer, the 3rd nylon layer and the 4th nylon layer, and described each layer is all through biaxial tension; Wherein, described first nylon layer and the 4th nylon layer are made up of nylon 95 ~ 100% and additive 0 ~ 5%, and described additive is a kind of in opening agent, slipping agent, antistatic additive or their combination; Described second nylon layer and the 3rd nylon layer are the nylon of 100%; Described evoh layer is the EVOH of 100%.
Wherein, the first described nylon layer, second nylon layer, 3rd nylon layer, the nylon that 4th nylon layer uses can be: nylon 6(PA6), polyhexamethylene adipamide (PA66), MC nylon, RIM nylon, poly-certain herbaceous plants with big flowers two acyl certain herbaceous plants with big flowers diamines (PA1010), poly-11 lactams (PA11), nylon 12 (PA12), nylon 46 (PA46), poly-certain herbaceous plants with big flowers two acyl hexamethylene diamine (PA610), poly-hexamethylene dodecanamide (PA612), poly-dodecanoyl lauryl amine (PA1212), poly-m-phenylene adipamide (MXD6), poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T), a kind of in poly-hexamethylene terephthalamide (PA6T) or their combination.Preferred nylon 6(PA6).
The scope of the ethylene molar content of described EVOH can be: 24mol% ~ 48mol%.Wherein, preferred ethylene molar content is 27mol% ~ 32mol%, and preferred content is 32mol%.
Described opening agent can be silica, calcium carbonate, talcum powder, the one in glass microballoon or its combination.
Described slipping agent can be one in erucyl amide, stearic acid erucyl amide, the two fatty acid acid amides of ethylene, oleamide, vinyl bis-stearamides, organic silicone oil or its combination.
Described antistatic additive can be alkyl phosphate diethanolamine salt, alcohol ether phosphate monoester, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, two (2-hydroxyethyl)-the N-(3 '-dodecyloxy-2 of N, N-'-hydroxypropyl) methylamine Methylsulfate salt, one in trihydroxyethyl methyl amine Methylsulfate salt or its combination.
The thickness range of biaxial tension EVOH/ coextrusion nylon film of the present invention is 10 ~ 25 μm.
Wherein, described evoh layer thickness is 1 ~ 5 μm, preferably 2 ~ 3 μm;
Wherein, described first nylon layer can be consistent with the 4th nylon layer thickness, is 1 ~ 2.5 μm separately, preferably 2 μm.
Biaxial tension EVOH/ coextrusion nylon film of the present invention preferably has a surface at least through sided corona treatment.
The present invention also provides a kind of preparation method of biaxial tension EVOH/ coextrusion nylon film, comprises following operation:
The first step, by corresponding to the layers of material of the first nylon layer, the second nylon layer, evoh layer, the 3rd nylon layer and the 4th nylon layer by extruder heating and melting, coextrusion, makes melt be cooled to slab on sharp cooling roll;
Second step, slab through 40 ~ 60 DEG C of water-bath preheatings, then carries out conditioning through the water-bath of 60 ~ 75 DEG C, is dried up by slab surface moisture after terminating;
3rd step, carries out biaxial tension to slab;
4th step, the film after stretching is through thermal finalization process;
5th step, rolling product;
Wherein, described first nylon layer and the 4th nylon layer are made up of nylon 95 ~ 100% and additive 0 ~ 5%, described additive is a kind of in opening agent, slipping agent, antistatic additive or their combination, described second nylon layer and the 3rd nylon layer are the nylon of 100%, and described evoh layer is the EVOH of 100%.
Preferably, the technique of described biaxial tension is mechanical retractable arm principle synchro-draw technique or linear electric machine synchro-draw technique.
Further, when the technique of described biaxial tension is linear electric machine synchro-draw technique, slab directly can carry out biaxial tension without second step operation.
Preferably, after described 4th step thermal finalization process, give film to a certain degree lax, lax ratio is 3 ~ 7%.
The first nylon layer described in described preparation method, second nylon layer, 3rd nylon layer, the nylon that 4th nylon layer uses can be: nylon 6(PA6), polyhexamethylene adipamide (PA66), MC nylon, RIM nylon, poly-certain herbaceous plants with big flowers two acyl certain herbaceous plants with big flowers diamines (PA1010), poly-11 lactams (PA11), nylon 12 (PA12), nylon 46 (PA46), poly-certain herbaceous plants with big flowers two acyl hexamethylene diamine (PA610), poly-hexamethylene dodecanamide (PA612), poly-dodecanoyl lauryl amine (PA1212), poly-m-phenylene adipamide (MXD6), poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T), a kind of in poly-hexamethylene terephthalamide (PA6T) or their combination.Preferred nylon 6(PA6).
The scope of the ethylene molar content of described EVOH can be: 24mol% ~ 48mol%.Wherein, preferred ethylene molar content is 27mol% ~ 32mol%.Preferred, the ethylene molar content of described EVOH is 32mol%
Described opening agent can be one in silica, calcium carbonate, talcum powder, glass microballoon or its combination.
Described slipping agent can be one in erucyl amide, stearic acid erucyl amide, the two fatty acid acid amides of ethylene, oleamide, vinyl bis-stearamides, organic silicone oil or its combination.
Described antistatic additive can be alkyl phosphate diethanolamine salt, alcohol ether phosphate monoester, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, two (2-hydroxyethyl)-the N-(3 '-dodecyloxy-2 of N, N-'-hydroxypropyl) methylamine Methylsulfate salt, one in trihydroxyethyl methyl amine Methylsulfate salt or its combination.
The thickness range of the biaxial tension EVOH/ coextrusion nylon film described in preparation method of the present invention is 10 ~ 25 μm.
Wherein, described evoh layer thickness is 1 ~ 5 μm, preferably 2 ~ 3 μm;
Wherein, described first nylon layer can be consistent with the 4th nylon layer thickness, is 1 ~ 2.5 μm separately, preferably 2 μm.
In preparation method provided by the invention, preferably in the 5th step operation, sided corona treatment is carried out at least one surface of film.
Biaxial tension EVOH/ coextrusion nylon film proposed by the invention has excellent mechanical property and barrier property, in barrier property than BON biaxially oriented nylon film advantageously, and the EVOH co-extrusion film that mechanical property does not stretch especially is incomparable for this composite membrane.
The present invention also proposes a kind of method preparing biaxial tension EVOH/ coextrusion nylon film simultaneously, and the method makes the biaxial tension of EVOH easily implement.
accompanying drawing illustrates:
Accompanying drawing 1 is the structural representation of biaxial tension EVOH/ coextrusion nylon film of the present invention.
detailed description of the invention:
Further describe below in conjunction with the drawings and specific embodiments, but therefore do not limit the present invention in described scope of embodiments.
Fig. 1 is the five-layer structure schematic diagram of biaxial tension EVOH/ coextrusion nylon film of the present invention.As shown in Figure 1, composite membrane of the present invention is followed successively by the 4th nylon layer 5 of the first nylon layer 1 of biaxial tension, the second nylon layer 2 of biaxial tension, the evoh layer 3 of biaxial tension, the 3rd nylon layer 4 of biaxial tension and biaxial tension from top to bottom.
Wherein, described first nylon layer and the 4th nylon layer are made up of nylon 95 ~ 100% and additive 0 ~ 5%, and described additive is a kind of in opening agent, slipping agent, antistatic additive or their combination; In the present invention, processing, the serviceability that additive can improve film is to a certain extent added to two nylon top layers, its addition should consider the factors such as effect, demand and financial cost, and the additive in the present invention in the first nylon layer and the 4th nylon layer is advisable to be no more than 5%.Described second nylon layer and the 3rd nylon layer are the nylon of 100%; Described evoh layer is the EVOH of 100%.
The first described nylon layer, second nylon layer, 3rd nylon layer, the nylon that 4th nylon layer uses can be: nylon 6(PA6), polyhexamethylene adipamide (PA66), MC nylon, RIM nylon, poly-certain herbaceous plants with big flowers two acyl certain herbaceous plants with big flowers diamines (PA1010), poly-11 lactams (PA11), nylon 12 (PA12), nylon 46 (PA46), poly-certain herbaceous plants with big flowers two acyl hexamethylene diamine (PA610), poly-hexamethylene dodecanamide (PA612), poly-dodecanoyl lauryl amine (PA1212), poly-m-phenylene adipamide (MXD6), poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T), a kind of in poly-hexamethylene terephthalamide (PA6T) or their combination.Wherein, nylon 6(PA6) be preferred.
Described EVOH refers to ethylene-vinyl alcohol copolymer, and the molar content of ethene determines barrier property and the processing characteristics of evoh layer.The present inventor finds, for realizing technique effect of the present invention better, preferred ethylene molar content is: 24mol% ~ 48mol%.Preferred, the molar content of ethene is 27mol% ~ 32mol%.Preferred content is 32mol%.
Described opening agent can be one in silica, calcium carbonate, talcum powder, glass microballoon or its combination.
Described slipping agent can be one in erucyl amide, stearic acid erucyl amide, the two fatty acid acid amides of ethylene, oleamide, vinyl bis-stearamides, organic silicone oil or its combination.
Described antistatic additive can be alkyl phosphate diethanolamine salt, alcohol ether phosphate monoester, as stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, two (2-hydroxyethyl)-the N-(3 '-dodecyloxy-2 of N, N-'-hydroxypropyl) methylamine Methylsulfate salt, one in trihydroxyethyl methyl amine Methylsulfate salt or its combination.
The thickness range of biaxial tension EVOH/ coextrusion nylon film of the present invention is 10 ~ 25 μm.Wherein, described evoh layer thickness is 1 ~ 5 μm, preferably 2 ~ 3 μm; Wherein, described first nylon layer can be consistent with the 4th nylon layer thickness, is 1 ~ 2.5 μm separately, preferably 2 μm.
Biaxial tension EVOH/ coextrusion nylon film of the present invention has a surface at least through sided corona treatment.
The present invention also provides a kind of preparation method of biaxial tension EVOH/ coextrusion nylon film, comprises following operation:
The first step, to the layers of material of the first nylon layer, the second nylon layer, evoh layer, the 3rd nylon layer and the 4th nylon layer be corresponded to by extruder heating and melting, wherein the processing temperature of nylon layer is suitable with common BOPA processing temperature, between 240 DEG C ~ 260 DEG C; The processing temperature of evoh layer is arranged between 210 DEG C ~ 220 DEG C, and such as can arrange each district temperature is 210 DEG C, 215 DEG C, 220 DEG C, 215 DEG C, 215 DEG C, 215 DEG C; Extruded by five layers of die head, make melt be cooled to slab on sharp cooling roll.Five extruder coextrusion or three extruder coextrusion can be adopted, preferably three extruder coextrusion: wherein the first nylon layer and the 4th nylon layer share an extruder, second nylon layer and the 3rd nylon layer share an extruder, and evoh layer uses an extruder.
Second step, slab through 40 ~ 60 DEG C of water-bath preheatings, then carries out conditioning through the water-bath of 60 ~ 75 DEG C, is dried up by slab surface moisture after terminating.Specifically, by slab through the preheating of 40 ~ 60 DEG C of water baths one, then can carry out conditioning through the water bath two of 60 ~ 75 DEG C, slab is generally advisable with 1min ~ 2min through water bath one and water bath two total time.The surface moisture of slab is dried up, enters subsequent processing, air knife can be used to carry out drying up operation.
3rd step, carries out biaxial tension to slab.Because EVOH is very easy to crystallization, so make follow-up cross directional stretch be difficult to carry out after longitudinal stretching due to highly crystalline.Therefore, the present invention operates preferably by synchro-draw, and mechanical retractable arm principle synchro-draw technique or linear electric machine synchro-draw technique (LISIM) specifically can be adopted to complete.Drawing process comprises preheating and stretches two stages, and preheat temperature is set to 80 DEG C
,draft temperature is set to 115 DEG C.
Especially, if when adopting linear electric machine synchro-draw technique, slab directly can carry out biaxial tension without second step operation.
4th step, the film after stretching is through thermal finalization process, and setting temperature is 210 DEG C.In order to make film have low thermal contraction ratio, preferably give its to a certain degree lax, lax ratio is 3 ~ 7%.
5th step, rolling product.This step can use conventional winder rolling product.Preferably, in this step, sided corona treatment is carried out at least one surface of film.
In this preparation method, the nylon that the first described nylon layer uses to the 4th nylon layer, the molar content of ethene in EVOH, the concrete selection of described opening agent, slipping agent, antistatic additive, the parameters such as the thickness of each layer of described biaxial tension EVOH/ coextrusion nylon film can be selected by the relevant parameter of product provided by the invention to confirm, repeat no more herein.
Product of the present invention and preparation method is further illustrated below in conjunction with embodiment.
Embodiment 1-5
Use nylon 6(PA6) and the EVOH of ethylene molar content 24 ~ 48mol%, employing LISIM technology the test of line correlation project of going forward side by side according to above-mentioned preparation method's preparing product, design parameter and test result are in table 1.
Comparative example 1-2
Comparative example 1 is the BOPA product of commercially available 15 μm of specifications.
Comparative example 2 is the commercially available EVOH co-extrusion film do not stretched, and its membrane structure is: PA (thickness is 20 μm)/EVOH (thickness is 10 μm)/tie(thickness is 1 μm)/PE (thickness is 59 μm).
The relevant parameter of comparative example 1,2 and test result are in table 1.
From table 1 and 2, biaxial tension EVOH/ coextrusion nylon film of the present invention have excellent mechanical property, particularly tear-resistant power be BOPA and the EVOH co-extrusion film that do not stretch incomparable, product of the present invention has lower mist degree index, transparency excellence.Meanwhile, its barrier property is also very excellent, compares the EVOH co-extrusion film that do not stretch, and thinner evoh layer also can reach the performance of high-barrier, therefore on cost advantageously.
Claims (25)
1. a biaxial tension nylon composite membrane, has following structure: the first nylon layer, the second nylon layer, evoh layer, the 3rd nylon layer and the 4th nylon layer, and described each layer is all through biaxial tension; Wherein, described first nylon layer and the 4th nylon layer are made up of nylon 95 ~ 100% and additive 0 ~ 5%, and described additive is a kind of in opening agent, slipping agent, antistatic additive or their combination; Described second nylon layer and the 3rd nylon layer are the nylon of 100%; Described evoh layer is the EVOH of 100%, and the scope of its ethylene molar content is: 24mol% ~ 48mol%; The thickness of described composite membrane is 10 ~ 25 μm, and the thickness of wherein said evoh layer is 1 ~ 5 μm, and described first nylon layer and the 4th nylon layer consistency of thickness are 1 ~ 2.5 μm; The tear-resistant power of transverse direction of described biaxial tension nylon composite membrane is 256 ~ 337mN, and longitudinally tear-resistant power is 269 ~ 360mN, and has 0.51 ~ 0.72CC/m
2.day.atm oxygen transmission rate.
2. biaxial tension nylon composite membrane according to claim 1, it is characterized in that, described nylon is one in nylon 6, polyhexamethylene adipamide, MC nylon, RIM nylon, poly-certain herbaceous plants with big flowers two acyl certain herbaceous plants with big flowers diamines, poly-11 lactams, nylon 12, nylon 46, poly-certain herbaceous plants with big flowers two acyl hexamethylene diamine, poly-hexamethylene dodecanamide, poly-dodecanoyl lauryl amine, poly-m-phenylene adipamide, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-hexamethylene terephthalamide or its combination.
3. biaxial tension nylon composite membrane according to claim 2, is characterized in that, described nylon is nylon 6.
4. biaxial tension nylon composite membrane according to claim 1, is characterized in that, the scope of the ethylene molar content of described EVOH is: 27mol% ~ 32mol%.
5. biaxial tension nylon composite membrane according to claim 4, is characterized in that, the ethylene molar content of described EVOH is 32mol%.
6. biaxial tension nylon composite membrane according to claim 1, is characterized in that, described opening agent is one in silica, calcium carbonate, talcum powder, glass microballoon or its combination.
7. biaxial tension nylon composite membrane according to claim 1, is characterized in that, described slipping agent is one in erucyl amide, stearic acid erucyl amide, the two fatty acid acid amides of ethylene, oleamide, vinyl bis-stearamides, organic silicone oil or its combination.
8. biaxial tension nylon composite membrane according to claim 1, it is characterized in that, described antistatic additive is alkyl phosphate diethanolamine salt, alcohol ether phosphate monoester, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, two (2-hydroxyethyl)-the N-(3 '-dodecyloxy-2 of N, N-'-hydroxypropyl) methylamine Methylsulfate salt, one in trihydroxyethyl methyl amine Methylsulfate salt or its combination.
9. the biaxial tension nylon composite membrane in claim 1-8 described in arbitrary claim, is characterized in that, the thickness of described evoh layer is 2 ~ 3 μm.
10. biaxial tension nylon composite membrane according to claim 9, is characterized in that, described first nylon layer and the 4th nylon layer thickness are all 2 μm.
11. biaxial tension nylon composite membranes according to claim 1, is characterized in that, described composite membrane has a surface at least through sided corona treatment.
The preparation method of 12. 1 kinds of biaxial tension nylon composite membranes, comprising:
The first step, by corresponding to the layers of material of the first nylon layer, the second nylon layer, evoh layer, the 3rd nylon layer and the 4th nylon layer by extruder heating and melting, coextrusion, makes melt be cooled to slab on sharp cooling roll;
Second step, slab through 40 ~ 60 DEG C of water-bath preheatings, then carries out conditioning through the water-bath of 60 ~ 75 DEG C, is dried up by slab surface moisture after terminating;
3rd step, carries out biaxial tension to slab;
4th step, the film after stretching is through thermal finalization process;
5th step, rolling product;
Wherein, described first nylon layer and the 4th nylon layer are made up of nylon 95 ~ 100% and additive 0 ~ 5%, described additive is a kind of in opening agent, slipping agent, antistatic additive or their combination, described second nylon layer and the 3rd nylon layer are the nylon of 100%, described evoh layer is the EVOH of 100%, and the scope of its ethylene molar content is: 24mol% ~ 48mol%; The thickness of described composite membrane is 10 ~ 25 μm, and the thickness of wherein said evoh layer is 1 ~ 5 μm, and described first nylon layer and the 4th nylon layer consistency of thickness are 1 ~ 2.5 μm; The tear-resistant power of transverse direction of described biaxial tension nylon composite membrane is 256 ~ 337mN, and longitudinally tear-resistant power is 269 ~ 360mN, and has 0.51 ~ 0.72CC/m
2.day.atm oxygen transmission rate.
13. preparation methods according to claim 12, is characterized in that, the technique of described biaxial tension is mechanical retractable arm principle synchro-draw technique or linear electric machine synchro-draw technique.
14. preparation methods according to claim 13, is characterized in that, when the technique of described biaxial tension is linear electric machine synchro-draw technique, slab directly can carry out biaxial tension without second step operation.
15. preparation methods according to claim 12, is characterized in that, after described 4th step thermal finalization process, give film to a certain degree lax, lax ratio is 3 ~ 7%.
Preparation method in 16. claim 12-15 described in arbitrary claim, it is characterized in that, described nylon is one in nylon 6, polyhexamethylene adipamide, MC nylon, RIM nylon, poly-certain herbaceous plants with big flowers two acyl certain herbaceous plants with big flowers diamines, poly-11 lactams, nylon 12, nylon 46, poly-certain herbaceous plants with big flowers two acyl hexamethylene diamine, poly-hexamethylene dodecanamide, poly-dodecanoyl lauryl amine, poly-m-phenylene adipamide, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-hexamethylene terephthalamide or its combination.
17. preparation methods according to claim 16, is characterized in that, described nylon is nylon 6.
Preparation method in 18. claim 12-15 described in arbitrary claim, is characterized in that, the scope of the ethylene molar content of described EVOH is 27mol% ~ 32mol%.
19. preparation methods according to claim 18, is characterized in that, the ethylene molar content of described EVOH is 32mol%.
Preparation method in 20. claim 12-15 described in arbitrary claim, is characterized in that, described opening agent is one in silica, calcium carbonate, talcum powder, glass microballoon or its combination.
Preparation method in 21. claim 12-15 described in arbitrary claim, it is characterized in that, described slipping agent is one in erucyl amide, stearic acid erucyl amide, the two fatty acid acid amides of ethylene, oleamide, vinyl bis-stearamides, organic silicone oil or its combination.
Preparation method in 22. claim 12-15 described in arbitrary claim, it is characterized in that, described antistatic additive is alkyl phosphate diethanolamine salt, alcohol ether phosphate monoester, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, two (2-hydroxyethyl)-the N-(3 '-dodecyloxy-2 of N, N-'-hydroxypropyl) methylamine Methylsulfate salt, one in trihydroxyethyl methyl amine Methylsulfate salt or its combination.
Preparation method in 23. claim 12-15 described in arbitrary claim, is characterized in that, the thickness of described evoh layer is 2 ~ 3 μm.
Preparation method in 24. claim 12-15 described in arbitrary claim, is characterized in that, described first nylon layer and the 4th nylon layer thickness are all 2 μm.
Preparation method in 25. claim 12-15 described in arbitrary claim, is characterized in that, in the 5th step operation, carrying out sided corona treatment at least one surface of film.
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| CN103554901B (en) * | 2013-10-22 | 2016-02-17 | 厦门长塑实业有限公司 | A kind of two-way stretching polyamide film masterbatch, film and manufacture method thereof |
| CN105218855B (en) * | 2015-10-27 | 2017-03-29 | 厦门长塑实业有限公司 | A kind of uvioresistant poly amide film and preparation method thereof |
| CN105566776A (en) * | 2016-01-21 | 2016-05-11 | 广西大学 | Electrical insulating material |
| CN106739335A (en) * | 2016-12-15 | 2017-05-31 | 厦门长塑实业有限公司 | A kind of super High-barrier nylon film and preparation method thereof |
| CN108515762B (en) * | 2018-04-08 | 2019-09-17 | 厦门长塑实业有限公司 | A kind of puncture-resistant BON biaxially oriented nylon film of three-decker and preparation method thereof |
| CN111907161B (en) * | 2020-07-13 | 2022-07-29 | 厦门长塑实业有限公司 | Transparent ultrahigh-barrier composite film and preparation method thereof |
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| CN101125933A (en) * | 2007-09-18 | 2008-02-20 | 佛山塑料集团股份有限公司 | Plastic film and preparation method thereof |
| CN202054245U (en) * | 2011-04-21 | 2011-11-30 | 江阴申恒特种新材料有限公司 | High-barrier multilayer packaging bag for meat products |
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| CN101125933A (en) * | 2007-09-18 | 2008-02-20 | 佛山塑料集团股份有限公司 | Plastic film and preparation method thereof |
| CN202054245U (en) * | 2011-04-21 | 2011-11-30 | 江阴申恒特种新材料有限公司 | High-barrier multilayer packaging bag for meat products |
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